US2343834A - Rubber hydrochloride - Google Patents

Rubber hydrochloride Download PDF

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Publication number
US2343834A
US2343834A US264779A US26477939A US2343834A US 2343834 A US2343834 A US 2343834A US 264779 A US264779 A US 264779A US 26477939 A US26477939 A US 26477939A US 2343834 A US2343834 A US 2343834A
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US
United States
Prior art keywords
rubber
ethylene
photochemical
parts
grams
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US264779A
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English (en)
Inventor
Scott Winfield
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wingfoot Corp
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Wingfoot Corp
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Filing date
Publication date
Priority to BE435601D priority Critical patent/BE435601A/xx
Application filed by Wingfoot Corp filed Critical Wingfoot Corp
Priority to US264779A priority patent/US2343834A/en
Priority to FR858027D priority patent/FR858027A/fr
Application granted granted Critical
Publication of US2343834A publication Critical patent/US2343834A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/925—Natural rubber compositions having nonreactive materials, i.e. NRM, other than: carbon, silicon dioxide, glass titanium dioxide, water, hydrocarbon or halohydrocarbon

Definitions

  • Rubber hydrohalides such as rubber hydrochloride
  • Rubber hydrohalides have been known for many years and, in recent years, have become commercially useful.
  • the invention is particularly applicable to rubber hydrochloride.
  • photochemical inhibitors are known which will markedly increase the life of rubber hydrohalides exposed to ultra-violet light, most of these possess certain inherent characteristics which, in some instances, are very objectionable. For example, some of them are incompatible with the rubber hydrohalide and tend to blush or "bloom out. Some of them are fugitive so that, although they are effective in freshly prepared rubberhydrohalide, they are eventually lost, .and their inhibiting eifect with them. The compatibility and relative permanence of these photochemical inhibitors are markedly afiected by the use of various plasticizers in the rubber hydrohalide. For example, some inhibitors are entirely satisfactory in unplasticized rubber hydrohalides but tend to "bloom out in plasticized mixtures, i.
  • Plasticizers are desirable components of rubber hydrohalide mixes for the manufacture of many a1- ticles, particularly in the form of film, which are normally exposed to sunlight, e. g., window curtains, wrapping materia1s,,etc., in order to give a softer "feel to the rubber hydrohalide and increase its tear resistance;
  • Thepreferred inhibitors of this invention are, therefore, those which are compatible withplasticized films or zoo-735i not form a bloom on such material on standing or ageing.
  • the preferred plasticizers for such use are butyl stearate or other alkyl esters of fatty acids, dibutyl phthalate or other alkyl esters of phthalic acid or a hydrogenated phthalic acid, and ethyl abietate or other ester of an acid derived from a vegetable oil.
  • Suitable plasticizers are propyl stearate, amyl stearate, hexyl stearate, heptyl stearate, decyl stearate, cyclohexyl stearate, glycol stearate, glyceryl stearate, ethyl oleate, butyl oleate, heptyl oleate, butyl palmitate, the propyl, amyl, heptyl, octyl, etc. esters of phthalic and hydrogenated phthalic acids, tributyl phosphate, triphenyl phosphate, and triphenyl thiophosphate.
  • plasticizers which impart tear-resistance to rubber hydrohalides, are. described in U. S. application Serial No. 102,223, filed September 23, 1936 inthe name of Calvert.
  • a new class of photochemical inhibitors for rubber hydrohalides has been discovered, the members of which have a number of very desirable characteristics. They efiectively resist the deteriorating efl'ect of light and the preferred members of the class are highly compatible with the rubber hydrohalide and are substantially permanent and non-fugitive in plasticized or unplasticized rubber hydrohalides.
  • a triethylene tetramine may then be formed by any of the following processes (a) RNH-CQHr-N- OlHG-NE-R+BPCQ PNHR By successive reactions similar to those above,,
  • these ethylene poiyamines may build up to compounds of very high molecular weight
  • cyclic compounds may be similarly formed by ioinder of the terminal secondary amino groups by reaction with ethylene bromide.
  • Compounds of the class type indicated above may also be prepared by reacting diethylene triamine, trietlrylene-tetramlne, etc. with a suitable alwl halide as illustrated by the following equa- ,Two hundred eighty-two parts (2.5 mols) of o-methyl cyclohexylamine were placed in a reactor equipped with a stirrer, a reflux condenser and a thermometer and the charge was heated to about 100 C. About 10% of the total charge of 192 parts (1.02 mol) of ethylene dibromide was run in slowly and was allowed to react. A portion (5-10% of the total) of the. caustic used to neutralize the hydrobromic acid formed in the reaction was then added.
  • a suitable alwl halide as illustrated by the following equa- ,Two hundred eighty-two parts (2.5 mols) of o-methyl cyclohexylamine were placed in a reactor equipped with a stirrer, a
  • fraction 2 contained the ethylene diamine and piperazine derivatives.
  • Fraction 3 contained high molecular compounds having the desired inhibiting properties.
  • the amine was placed in a flask equipped with a stirrer, a reflux condenser, and a dropping funnel and heated to about 125 C. Ethylene bromide was then slowly added through the dropping funnel. -To prevent crystallization of amine hydrobroinide formed during the reaction, a few cc. of water were added through the condenser from time to time. When about half the ethylene dibromide'had been added, the mixture was heated to 120-130 C. for 10 minutes and about 90 grams of sodium hydroxide dissolved in 167 cc. of water were slowly added. The remainder of the ethylene dibromide was added as before and, after heating 10-15 minutes at 0., about grams of sodium hydroxide dissolved in 334 cc. of water were slowly added. The mixture was then maintained at 115-120 C. for one hour. The oily layer was separated from sure.
  • EXAMPLE 5 The N,N'di(o-methyl cyclohexyl) ethylene diamine obtained in Example 4 in the 257 gram fraction boiling at ISO-205 C. at 6-7 mm. pressure can be utilized in preparing succeeding from time to time to prevent crystallization.
  • EXAMPLE 6 A mixture of 200 grams of N,N'di(o-methyl cyclohexyl) ethylene diamine, 135 grams of 0- methyl cyclohexylamine, 99 grams of ethylene dichloride, and 200 cc. of water was placed in a steel autoclave and heated at 200 for one-half hour. The reaction mixture was cooled to about 100 C., at which temperature it was completely liquid, and was treated with a mixture of 90 grams of sodium hydroxide and 100 cc. of water and boiled for one-half hour. The oily portion was then separated, washed with water and distilled at 5 mm. pressure to give the following fractions:
  • alkylene' polyhalides which may be used are n-propylene dibromide, 1,2-dibromopropane, 1-2, 1-3 and '1-4 dichlor or di-brom'butane, the dior tri-halogen derivatives of the pentanes, dichlorhydrin, di- (chlorethyl) ether, and homologues of these compounds. Of these materials, those compounds in which the alkylene groups are hydrocarbon i groups are preferred.
  • the residue was a brown, viscous oil possessing the desired photo-chemical inhibiting properties.
  • EXAMPLE 7 Eight hundred grams (8.1 .mols) of cyclohcxylamine, mixed with 100 cc. of water, were treated with 564 grams (3 mols) of ethylene di-v bromide at a temperature rising from 100 C. to 120 C. Then about 5 3 of a solution of 540 grams Y of sodium hydroxide dissolved in 1000 cc. of Water was added, followed after heating and stirring Any primary aliphatic amine may be employed, including straight or branched chain amines, cycloaliphatic amines, such as cyclohexyamine, and ring substituted aliphatic amines, such as hexylamine, the heptylamines, the nonylamines,
  • reaction may take, substantially any proportions of reactants may be employed. Also, the temperature, pressure and other conditions of the Further exv reaction may be varied ⁇ greatly while still obtaming materials coming within the invention.
  • suitable for direct useand is a very effective photochemical inhibitor and constitutes a preferred iorm "oflthe invention.
  • these materials are relatively more permanent than previously known inhibitors, this improvement being particularly noticeable in film containing added plasticizers such as butyl stearate and dibutyl phthalate.
  • Rubber hydrochloride containing a photochemical inhibitor which is a reaction product of I Rubber hydrochloride containing, as a photochemical inhibitor, the-composite product obtained by reacting an alkylene polyhalide with a primary aliphatic amine and freeing the reaction product from any contained alkylene polyamines, piperazines and unreacted starting materials.
  • Rubber hydrochloride containing as a photochemical inhibitor the composite product obtained by reacting an ethylene dihalide with a primary aliphatic amine and freeing the resultant reaction product from unreacted starting materials and by-product dii'aliphatic) ethylene diamine and N,N'di(aliphatic) piperazine.
  • Rubber hydrochloride containing a photochemical inhibitor which is a reaction product of an alkylene dihalide and a primary aliphatic amine, the said product containing more than two aliphatic substituted nitrogen atoms and having nitrogen to nitrogen linkages efi'ected through alkylene groups.
  • Rubber hydrochloride containing, as a photochemical inhibitor, a polyalkylene polyamine in which each of the amino nitrogen atoms contains one aliphatic substituent in addition to the connecting alkylene groups.
  • a fllm comprising rubber hydrochloride and a plasticizer which increases the tear-resistance oi the film and a photochemical inhibitor which is a reaction product of an alkylene dihalide and a primary aliphatic amine, the said product containing more than two aliphatic substituted nitro-- gen atoms and having nitrogen to nitrogen linkages efiected through alkylene groups and being sufliciently compatible with the plasticized rubber in which R and R: are aliphatic radicals, R1 is selected from the group consisting of hydrogen and aliphatic radicals, R3 and R4 are alkylene groups and a: is a. whole number.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US264779A 1939-03-29 1939-03-29 Rubber hydrochloride Expired - Lifetime US2343834A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BE435601D BE435601A (en)) 1939-03-29
US264779A US2343834A (en) 1939-03-29 1939-03-29 Rubber hydrochloride
FR858027D FR858027A (fr) 1939-03-29 1939-07-20 Procédé de stabilisation du chlorhydrate et d'autres hydrohalogénures de caoutchouc et produits en résultant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US264779A US2343834A (en) 1939-03-29 1939-03-29 Rubber hydrochloride

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US2343834A true US2343834A (en) 1944-03-07

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FR (1) FR858027A (en))

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2561011A (en) * 1949-07-13 1951-07-17 Wingfoot Corp Nonfogging rubber hydrochloride film and method of making it
US2870152A (en) * 1959-01-20 Unilcu

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2870152A (en) * 1959-01-20 Unilcu
US2561011A (en) * 1949-07-13 1951-07-17 Wingfoot Corp Nonfogging rubber hydrochloride film and method of making it

Also Published As

Publication number Publication date
FR858027A (fr) 1940-11-15
BE435601A (en))

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